Black carbon aerosol and carbon monoxide in European regionally polluted air masses at Mace Head, Ireland during 1995–1998

Continuous measurements of black carbon aerosol (BCA) at the Mace Head Atmospheric Research Station on the Atlantic Ocean coast of Ireland show the occurrence of dramatically elevated concentrations when regionally polluted air masses are advected to the station. These occurrences correlate well with similar elevations in carbon monoxide and a wide range of other trace gases monitored near-simultaneously with the BCA. Using daily sector allocation and a sophisticated Lagrangian dispersion model, two independent estimates of the European emission source strength of BCA that are required to explain the Mace Head observations have been made. The best estimates of the UK and European emission source strengths of BCA are 46±14 and [(482–511)±140]×10³ tonnes yr⁻¹, respectively, and these estimates compare favourably with published inventories, at least to within ±25%, though they are considerably smaller than the emissions employed in some early global climate model studies.     

The seasonal cycles and photochemistry of C2–C5 alkanes at Mace Head

Continuous in-situ measurements of NMHCs at Mace Head, Ireland during two full annual cycles from January 2005 to January 2007 were used to investigate NMHC emission sources and transport including dilution and photochemical oxidation. The Mace Head research station is ideally located to sample a wide range of air masses including polluted European transport, clean North Atlantic and Arctic air masses and the ultra-clean, Southern Atlantic air masses. The variety in air mass sampling is used to investigate interaction of emissions, transport, dilution and photochemistry. Variability of long-lived hydrocarbon ratios is used to assess and estimate typical transport times from emission source to the Mace Head receptor. Seasonality in the ratios of isomeric alkane pairs (for butane and pentanes) are used to assess the effects of atmospheric transport and photochemical ageing. Finally, the natural logarithms of NMHC ratios are used to assess photochemical oxidation.     

Methane emissions from peat bogs in the vicinity of the Mace Head Atmospheric Research Station over a 12-year period

Methane emissions from the peat bogs in Connemara, Ireland have been inferred from the trace gas observations at the Mace Head Atmospheric Research Station using the nocturnal box method. A total of 237 local events, during April to September, over a 12-year period have been studied. Simultaneous emissions of methane, carbon dioxide and chloroform are routinely observed under nocturnal inversions with low wind speeds from the peat bogs proximal to Mace Head. Night-time deposition of ozone and hydrogen occurs concurrently with these emissions. Using the temporally correlated methane and ozone data we estimate methane emissions from each event. Simultaneous methane and chloroform emissions, together with ozone and hydrogen deposition have been characterised, leading to the estimation of methane emission rates for each event. The mean methane emission flux was found to be 400 ± 90 ng m^?2 s^?1. A strong seasonal cycle was found in the methane emission fluxes but there was little evidence of a long-term trend in the emissions from the peat bogs in the vicinity of the Mace Head station.     

Sources and source variations for aerosol at Mace Head,Ireland

The sources and source variations for aerosol at Mace Head, Ireland, were studied by applying positive matrix factorization (PMF), a variant of factor analysis, to a 5-yr data set for bulk aerosol. Signals for the following six sources were evident year round: (1) mineral dust, (2) sea salt, (3) general pollution, (4) a secondary SO₄²⁻–Se signal that is composed of both natural (marine) and pollution (coal) components, (5) ferrous industries, (6) and a second marine (possibly biogenic) source. Analyses of seasonally stratified data suggested additional sources for iodine and oil emissions but these were present only in certain seasons, respectively. The marine signal is particularly strong in winter. The main pollution transport from Europe to Mace Head occurs in May, but the influence of continental European emissions is evident throughout the year. Mineral aerosol evidently follows a transport pathway similar to that of pollution aerosol, i.e., recirculation via the westerlies brings pollutants mixed with dust to the site from nearby land, i.e., Ireland, the United Kingdom, and the Belgium, Netherlands, and Luxemburg (Benelux) region, with some inputs from Scandinavia, Western Europe, Eastern Europe, and even the Mediterranean region. Compared with Bermuda, aerosol at Mace Head has stronger marine sources (especially marine-derived secondary SO₄²⁻ and Se) but weaker crustal and oil signals. Transport across the North Atlantic, especially in winter, cannot be ruled out.     

The phase-in and phase-out of European emissions of HCFC-141b and HCFC-142b under the Montreal Protocol: Evidence from observations at Mace Head,Ireland and Jungfraujoch,Switzerland from 1994 to 2004

The mixing ratios of HCFC-141b (1,1-dichlorofluoroethane) and HCFC-142b (1-chloro-1,1-difluoroethane) have been rising steadily in baseline air at Mace Head, Ireland over the 10-year period from 1994 to 2004. These HCFCs are widely used replacements for the chlorofluorocarbons phased out under the Montreal Protocol and its subsequent amendments. Analysis of the HCFC content of regionally-polluted air arriving at Mace Head from the European continent shows that European emissions reached a peak during 2000–2001 and have declined subsequently, following the phase-out in their usage. European emissions of HCFC-141b have been further constrained by observations at the High-Alpine Jungfraujoch site. The reductions are consistent with the phase-out of HCFC production and use from the year 2001 onwards mandated by European regulations designed to exceed the requirements of the Montreal Protocol.     

Volcanic sulphate and arctic dust plumes over the North Atlantic Ocean

High time resolution aerosol mass spectrometry measurements were conducted during a field campaign at Mace Head Research Station, Ireland, in June 2007. Observations on one particular day of the campaign clearly indicated advection of aerosol from volcanoes and desert plains in Iceland which could be traced with NOAA Hysplit air mass back trajectories and satellite images. In conjunction with this event, elevated levels of sulphate and light absorbing particles were encountered at Mace Head. While sulphate concentration was continuously increasing, nitrate levels remained low indicating no significant contribution from anthropogenic pollutants. Sulphate concentration increased about 3.8 μg m⁻³ in comparison with the background conditions. Corresponding sulphur flux from volcanic emissions was estimated to about 0.3 TgS yr⁻¹, suggesting that a large amount of sulphur released from Icelandic volcanoes may be distributed over distances larger than 1000 km. Overall, our results corroborate that transport of volcanogenic sulphate and dust particles can significantly change the chemical composition, size distribution, and optical properties of aerosol over the North Atlantic Ocean and should be considered accordingly by regional climate models.     

Diurnal cycles of short-lived tropospheric alkenes at a north Atlantic coastal site

Observation of diurnal cycles in atmospheric concentrations of reactive alkenes are reported from measurements performed at a North Atlantic coastal site (Mace Head, Eire 53°19′34″N; 9°54′14″W). Species seen to exhibit distinct cycles included isoprene, ethene, propene, 1-butene, iso-butene and a substituted C₆ alkene. Five hundred and thirty air mass classified measurements were performed over a 4 week period at approximately hourly frequency and demonstrate that during periods when air flow resulted from unpolluted oceanic regions a clear daily cycle in concentrations existed, peaking at around solar noon for all species. These observations support the proposed mechanism of production via photochemical degradation of organic carbon in sea water. The observed concentrations showed strong correlation (propene R²>0.75) with solar flux, with little relationship to other meteorological or chemical parameters. The species’ short atmospheric lifetimes indicate that the source of emission was from local coastal waters within close proximity of the sampling site. At solar noon concentrations of reactive alkenes from oceanic sources were responsible for up to 88% of non-methane hydrocarbon reaction with the hydroxyl radical at this coastal marine site.     

An analysis of condensation nuclei levels at Mace Head,Ireland

Condensation nuclei (CN) concentrations measured at Mace Head between 1990 and 1992 are presented. The background CN concentration was found to typically range from 100 to 700 cm^-3. Concentration values were in this range for 55% of the measurement period. No seasonal cycle was observed in the CN concentration values. Concurrent equivalent black carbon (EBC) measurements are used to examine anthropogenic influences on the background CN concentration. Evidence that transatlantic air mass transport influenced the background CN concentration, contributing to increased CN and EBC levels, is shown. During polluted conditions the CN concentration was generally higher than 1000 cm^-3. The principal source for high pollution levels was European air masses arriving at the site. Very high CN concentrations, greater than 50 000 cm^-3, are attributed to local gas-to-particle conversion processes. The characteristics of a number of particle production events are considered. These show that these events are highly photochemical and occur during both clean and polluted conditions. Such production events though infrequent contributed significantly to the total aerosol number concentration.     

The concurrent observation of methyl iodide and dimethyl sulphide in marine air; implications for sources of atmospheric methyl iodide

Continuous atmospheric measurements of methyl iodide and dimethyl sulphide were carried out at Mace Head, western Ireland, over a 4-week period in July 1996. The concurrent observations of methyl iodide and dimethyl sulphide reported here display a clear association, indeed statistical analysis indicated a very significant degree of covariance. A simple yet informative use of modelled 5-day back trajectories was employed in tandem with examination of local meteorology to illuminate the geographical source regions of methyl iodide and dimethyl sulphide. The interpretation of the atmospheric observations in terms of air-mass flow has elucidated part of the global methyl iodide cycle and provides evidence for two distinct source regions of methyl iodide:1. Under certain synoptic meteorological conditions, long-range transport of methyl iodide and dimethyl sulphide was observed from discrete areas of the sub-tropical Atlantic Ocean located in a region between 30–50°N and 20–50°W.2. Measurements taken under different conditions led us to believe that there was an additional source of methyl iodide that influenced the Mace Head atmosphere, most likely produced by coastal macroalgae which inhabit waters off the western coast of Ireland.     

The characteristics of ozone and related compounds in the boundary layer of the South China coast: temporal and vertical variations during autumn season

We present measurements of several trace gases made at a subtropical coastal site in Hong Kong in October and November 1997. The gases include O₃, CO, SO₂, and NO_x. The surface measurement data are compared with those from an aircraft study [Kok et al. J. Geophys. Res. 102 (D15) (1997) 19043–19057], and a subset of the latter is used to show the vertical distribution of the trace gases in the boundary layer. During the study period, averaged concentrations at the surface site for O₃, CO, NO_x, and SO₂ were 50, 298, 2.75, and 1.65 ppbv, respectively. Their atmospheric abundance and diurnal pattern are similar to those found in the “polluted” rural areas in North America. The measured trace gases are fairly well mixed in the coastal boundary layer in the warm South China region. Large variability is indicated from the data. Examination of 10-day, isentropic back trajectories shows that the measured trace gases are influenced by maritime air masses, outflow of pollution-laden continental air, and the mixing of the two. The trajectories capture the contrasting chemical features of the large-scale air masses impacting on the study area. CO, NO_x and SO₂ all show higher concentrations in the strong outflow of continental air, as expected, than those in the marine category. Compared with previously reported values for the western Pacific, the much higher levels found in the marine trajectories in our study suggest the impacts of regional and/or sub-regional emissions on the measured trace gases at the study site. The presence of abundant O₃ and other chemically active trace gases in the autumn season, coupled with high solar radiation and warm weather, suggests that the South China Sea is a photochemically active region important for studying the chemical transformation of pollutants emitted from the Asian continent.     

Global scale emission and distribution of sea-spray aerosol: Sea-salt and organic enrichment

The chemical composition of marine aerosols as a function of their size is an important parameter for the evaluation of their impact on the global climate system. In this work we model fine particle organic matter emitted by sea spray processes and its influence on the aerosol chemical properties at the global scale using the off-line global Chemistry-Transport Model TM5. TM5 is coupled to a microphysical aerosol dynamics model providing size resolved information on particle masses and numbers. The mass of the emitted sea spray particles is partitioned between water insoluble organic matter (WIOM) and sea salt components in the accumulation mode using a function that relates the emitted organic fraction to the surface ocean chlorophyll-a concentrations. The global emission in the sub-micron size range of organic matter by sea spray process is 8.2 Tg yr^?1, compared to 24 Tg fine yr^?1 sea-salt emissions. When the marine sources are included, the concentrations of modelled primary particulate organic matter (POM) increase mainly over the oceans. The model predictions of WIOM and sea salt are evaluated against measurements carried out at Mace Head (Northern Hemisphere) and Amsterdam Island (Southern Hemisphere), showing that in clean marine conditions WIOM marine emissions contribute significantly to POM values.     

A mobile pollutant measurement laboratory—measuring gas phase and aerosol ambient concentrations with high spatial and temporal resolution

A mobile pollutant measurement laboratory was designed and built at the Paul Scherrer Institute (Switzerland) for the measurement of on-road ambient concentrations of a large set of trace gases and aerosol parameters with high time resolution (<15 s for most instruments), along with geographical and meteorological information. This approach allowed for pollutant level measurements both near traffic (e.g. in urban areas or on freeways/main roads) and at rural locations far away from traffic, within short periods of time and at different times of day and year. Such measurements were performed on a regular base during the project year of gas phase and aerosol measurements (YOGAM). This paper presents data measured in the Zürich (Switzerland) area on a late autumn day (6 November) in 2001. The local urban particle background easily reached 50 000 cm⁻³, with additional peak particle number concentrations of up to 400 000 cm⁻³. The regional background of the total particle number concentration was not found to significantly correlate with the distance to traffic and anthropogenic emissions of carbon monoxide and nitrogen oxides. On the other hand, this correlation was significant for the number concentration of particles in the size range 50–150 nm, indicating that the particle number concentration in this size range is a better traffic indicator than the total number concentration. Particle number size distribution measurements showed that daytime urban ambient air is dominated by high number concentrations of ultrafine particles (nanoparticles) with diameters <50 nm, which are immediately formed by traffic exhaust and thus belong to the primary emissions. However, significant variation of the nanoparticle mode was also observed in number size distributions measured in rural areas both at daytime and nighttime, suggesting that nanoparticles are not exclusively formed by primary traffic emissions. While urban daytime total number concentrations were increased by a factor of 10 compared to the nighttime background, corresponding factors for total surface area and total volume concentrations were 2 and 1.5, respectively.     

Traffic and meteorological impacts on near-road air quality: summary of methods and trends from the Raleigh Near-Road Study

A growing number of epidemiological studies conducted worldwide suggest an increase in the occurrence of adverse health effects in populations living, working, or going to school near major roadways. A study was designed to assess traffic emissions impacts on air quality and particle toxicity near a heavily traveled highway. In an attempt to describe the complex mixture of pollutants and atmospheric transport mechanisms affecting pollutant dispersion in this near-highway environment, several real-time and time-integrated sampling devices measured air quality concentrations at multiple distances and heights from the road. Pollutants analyzed included U.S. Environmental Protection Agency (EPA)-regulated gases, particulate matter (coarse, fine, and ultrafine), and air toxics. Pollutant measurements were synchronized with real-time traffic and meteorological monitoring devices to provide continuous and integrated assessments of the variation of near-road air pollutant concentrations and particle toxicity with changing traffic and environmental conditions, as well as distance from the road. Measurement results demonstrated the temporal and spatial impact of traffic emissions on near-road air quality. The distribution of mobile source emitted gas and particulate pollutants under all wind and traffic conditions indicated a higher proportion of elevated concentrations near the road, suggesting elevated exposures for populations spending significant amounts of time in this microenvironment. Diurnal variations in pollutant concentrations also demonstrated the impact of traffic activity and meteorology on near-road air quality. Time-resolved measurements of multiple pollutants demonstrated that traffic emissions produced a complex mixture of criteria and air toxic pollutants in this microenvironment. These results provide a foundation for future assessments of these data to identify the relationship of traffic activity and meteorology on air quality concentrations and population exposures.     

Traffic and Meteorological Impacts on Near-Road Air Quality: Summary of Methods and Trends from the Raleigh Near-Road Study

Abstract

A growing number of epidemiological studies conducted worldwide suggest an increase in the occurrence of adverse health effects in populations living, working, or going to school near major roadways. A study was designed to assess traffic emissions impacts on air quality and particle toxicity near a heavily traveled highway. In an attempt to describe the complex mixture of pollutants and atmospheric transport mechanisms affecting pollutant dispersion in this near-highway environment, several real-time and time-integrated sampling devices measured air quality concentrations at multiple distances and heights from the road. Pollutants analyzed included U.S. Environmental Protection Agency (EPA)-regulated gases, particulate matter (coarse, fine, and ultrafine), and air toxics. Pollutant measurements were synchronized with real-time traffic and meteorological monitoring devices to provide continuous and integrated assessments of the variation of near-road air pollutant concentrations and particle toxicity with changing traffic and environmental conditions, as well as distance from the road. Measurement results demonstrated the temporal and spatial impact of traffic emissions on near-road air quality. The distribution of mobile source emitted gas and particulate pollutants under all wind and traffic conditions indicated a higher proportion of elevated concentrations near the road, suggesting elevated exposures for populations spending significant amounts of time in this microenvironment. Diurnal variations in pollutant concentrations also demonstrated the impact of traffic activity and meteorology on near-road air quality. Time-resolved measurements of multiple pollutants demonstrated that traffic emissions produced a complex mixture of criteria and air toxic pollutants in this microenvironment. These results provide a foundation for future assessments of these data to identify the relationship of traffic activity and meteorology on air quality concentrations and population exposures.     

Inhomogeneity of methane emissions from a dairy waste lagoon

Methane (CH₄) is the dominant greenhouse gas emitted by animal agriculture manure. Since the gas is relatively insoluble in water, it is concentrated in discrete bubbles that rise through waste lagoons and burst at the surface. This results in lagoon emissions that are inhomogeneous in both space and time. Emissions from a midwestern dairy waste lagoon were measured over 2 weeks to evaluate the spatial homogeneity of the source emissions and to compare two methods for measuring this inhomogeneous emission. Emissions were determined using an inverse dispersion model based on CH₄ concentrations measured both by a single scanning tunable diode laser (TDL) aimed at a series of reflectors and by flame ionization detection (FID) gas chromatography on line-sampled air. Emissions were best estimated using scanned TDL concentrations over relatively short optical paths that collectively span the entire cross-wind width of the source, so as to provide both the best capture of discrete plumes from the bursting bubbles on the lagoon surface and the best detection of CH₄ background concentrations. The lagoon emissions during the study were spatially inhomogeneous at hourly time scales. Partitioning the inhomogeneous source into two source regions reduced the estimated emissions of the overall lagoon by 57% but increased the variability. Consequently, it is important to assess the homogeneity of a source prior to measurements and final emissions calculation.

Implications: Plans for measuring methane emissions from waste lagoons must take into account the spatial inhomogeneity of the source strength. The assumption of emission source homogeneity for a low-solubility gas such as CH₄ emitted from an animal waste lagoon can result in significant emission overestimates. The entire breadth and length of the area source must be measured, preferably with multiple optical paths, for the detection of discrete plumes from the different emitting regions and for determining the background concentration. Other gases with similarly poor solubility in water may also require partitioning of the lagoon source area.     

Estimation of atmospheric trace metal emissions in Vilnius City, Lithuania, using vertical concentration gradient and road tunnel measurement data

A new approach for the estimation of trace metal emissions in Vilnius city was implemented, using vertical concentration profiles in the urban boundary layer and road tunnel measurement data. Heavy metal concentrations were examined in fine and coarse particle fractions using a virtual impactor (cut-off size diameter 2.5 μm). Negative vertical concentration gradients were obtained for all metals (Ba, Pb, V, Sb, Zn) and both fractions. It was estimated that the vertical concentration gradient was formed due to emissions from an area of about 12 km². Road tunnel measurements indicated that trace metal concentrations on fine particles were lower than those on coarse particles, which suggested that re-emitted road dust was highly enriched in trace metal due to historic emissions within the tunnel. Emission rates of different pollutants in the road tunnel were calculated using pollutant concentration differences at the tunnel entrance and exit and traffic flow data. Heavy metal emission rates from the area of Vilnius city were estimated using the vertical gradient of heavy metal concentrations and the coefficient of turbulent mixing, as derived from meteorological measurement data. The emission values calculated by the two different methods coincided reasonably well, which indicated that the main source of airborne trace metals in Vilnius city is traffic. The potential of the vertical concentration gradient method for the direct estimation of urban heavy metal emissions was demonstrated.     

Variation of the mixing state of Saharan dust particles with atmospheric transport

Mineral dust is an important aerosol species in the Earth’s atmosphere and has a major source within North Africa, of which the Sahara forms the major part. Aerosol Time of Flight Mass Spectrometry (ATOFMS) is first used to determine the mixing state of dust particles collected from the land surface in the Saharan region, showing low abundance of species such as nitrate and sulphate internally mixed with the dust mineral matrix. These data are then compared with the ATOFMS single particle mass spectra of Saharan dust particles detected in the marine atmosphere in the vicinity of the Cape Verde islands, which are further compared with those from particles with longer atmospheric residence sampled at a coastal station at Mace Head, Ireland. Saharan dust particles collected near the Cape Verde Islands showed increased internally mixed nitrate but no sulphate, whilst Saharan dust particles collected on the coast of Ireland showed a very high degree of internally mixed secondary species including nitrate, sulphate and methanesulphonate. This uptake of secondary species will change the pH and hygroscopic properties of the aerosol dust and thus can influence the budgets of other reactive gases, as well as influencing the radiative properties of the particles and the availability of metals for dissolution.     

Relationships between emission sources and air mass characteristics in East Asia during the TRACE-P period

Long-range transport of pollutants influenced by anthropogenic and natural emission sources in East Asia is investigated by using backward trajectory analysis along the NASA TRACE-P flight tracks and a numerical simulation with the three-dimensional chemical transport model (STEM-2k1). Observation-based regional distributions of trace gases are reconstructed using the observations obtained by measurements on board the DC-8 and P3-B aircrafts. Systematic features of the spatial distribution for each species are identified. It is found that the observed concentrations of CO and some NMHCs, and the ratios between these species, are highly associated with the source distribution features and their regional characteristics. Reconstructed fields of the observed and modeled ethane/CO and ethane/propane are found to reproduce well the estimated emission ratios in East Asia. We also investigated the time rate of change of the concentration of species and their ratio along the trajectory. From this analysis the propane/ethane and propane/acetylene ratios are shown to preserve their emission ratios during regional transport. However systematic differences in the propane vs. acetylene/CO relationships are found between the model and observation values. This analysis suggests that further efforts are needed to improve the estimates of biomass burning emissions in SE Asia. The results presented in this paper also suggest ways to further extend the capabilities to derive observation-based inventories.     

Determination of cadmium, zinc, copper, chromium and arsenic in crude oil cargoes

One of the sources of trace heavy metal elements in air is emission by the oil industry, either directly through stack emissions from refineries or indirectly from emissions of combustion of hydrocarbons. Emission estimates are based mainly on the trace metal content of the crude oil processed. From a literature study carried out at the beginning of the 1990s it became clear that data on the trace metal content of crudes were scarce and showed a very large scatter. For this reason a measurement programme to assess the occurrence and concentrations of a number of trace metals, i.e. Cadmium (Cd), Zinc (Zn), Copper (Cu), Chromium (Cr), and arsenic (As), in crudes which are regularly processed in the Netherlands, was set up. By drafting strict sampling protocols and by constructing a special sampling device, as many as possible of the additional contamination sources were avoided. The study suggests that sample contamination may explain a significant amount of the scatter and some of the high concentrations reported in the literature for certain metals. The measured variation in the concentrations of Cd, Zn, and Cu is thought to be due to associated water and/or sediment particles from the producing wells or that picked up during transport. The greater consistency in our measurements for Cr and As suggests that these metals are predominantly associated with the hydrocarbon matrix. Based on the results of this work, it can be concluded that emissions of Cd, Zn, Cu, Cr, and As by the oil industry in the Netherlands are most probably significantly lower than hitherto assumed.     

Quantitative trace analysis of polyfluorinated alkyl substances (PFAS) in ambient air samples from Mace Head (Ireland): A method intercomparison

A method intercomparison study of analytical methods for the determination of neutral, volatile polyfluorinated alkyl substances (PFAS) was carried out in March, 2006. Environmental air samples were collected in triplicate at the European background site Mace Head on the west coast of Ireland, a site dominated by ‘clean’ westerly winds coming across the Atlantic. Extraction and analysis were performed at two laboratories active in PFAS research using their in-house methods. Airborne polyfluorinated telomer alcohols (FTOHs), fluorooctane sulfonamides and sulfonamidoethanols (FOSAs/FOSEs) as well as additional polyfluorinated compounds were investigated. Different native and isotope-labelled internal standards (IS) were applied at various steps in the analytical procedure to evaluate the different quantification strategies. Field blanks revealed no major blank problems. European background concentrations observed at Mace Head were found to be in a similar range to Arctic data reported in the literature. Due to trace-levels at the remote site, only FTOH data sets were complete and could therefore be compared between the laboratories. Additionally, FOSEs could partly be included. Data comparison revealed that despite the challenges inherent in analysis of airborne PFAS and the low concentrations, all methods applied in this study obtained similar results. However, application of isotope-labelled IS early in the analytical procedure leads to more precise results and is therefore recommended.